Method of treating textile materials



United States Patent 3,505,003 METHOD OF TREATING TEXTILE MATERIALSWilliam J. Vullo, Tonawanda, N.Y., assignor to Hooker ChemicalCorporation, Niagara Falls, N.Y., a corporation of New York No Drawing.Filed Apr. 18, 1966, Ser. No. 543,082 Int. Cl. D06m 13/00, 13/26 US. Cl.8---120 10 Claims ABSTRACT OF THE DISCLOSURE A method for improvingwrinkle and flame resistance in textile materials by reacting thetextile materials with alkyl vinyl phosphonium salts in the presence ofa basic catalyst.

This invention relates to improved textile materials, including methodsfor preparing the same. More particularly it relates to a method fortreating textile materials to impart wrinkle or crease-resistance andflame resistance to the material.

In recent years, increasing emphasis has been placed on the treatment oftextile materials so as to render them crease and/ or wrinkle resistant.With many of the compositions which have been proposed for treatingtextile materials for this purpose, the hand of the material treated maybe adversely affected. In other instances, the treating materials usedmay give satisfactory Wrinkle resistance when the fabric is dry, whileimparting only moderate or poor wrinkle resistance when the fabric iswet, or vice versa. Accordingly, in the past it has been very difficultto provide a composition for treating textile materials to render themwrinkle resistant which provides both wet and dry wrinkle resistancewithout adversely altering the hand or feel of the fabric.

It is, therefore, an object of the present invention to provide animproved wrinkle and flame-resistant textile material.

A further object of the present invention is to provide an improvedmethod for treating textile materials so as to render themwrinkle-resistant and flame-resistant.

These and other objects will become apparent to those skilled in the artfrom the description of the invention which follows.

Pursuant to the above objects, the present invention includes a processfor treating textile materials to impart wrinkle resistance thereto,which process comprises reacting a textile material, in the presence ofa basic catalyst, with an alkyl vinyl phosphonium salt. Desirably, thealkyl vinyl phosphonium salt used has the formula:

wherein R is a lower alkyl group, having from about 1 to 6 carbon atoms,n is a number from 1 to 2, and X is halogen.

Textile materials which may be treated in accordance with the presentinvention include those comprising natural or synthetic polymers orblends of the same, which have functional groups, such as hydroxyl,amino, amido, carboxyl, thiol, and the like, which are capable ofreacting with activated vinyl groups. Suitable textile materialsinclude, for example, cellulosic materials, such as cotton, linen,paper, and rayon, and proteinaceous materials such as wool and silk. Inmany instances, it has been found that the cellulosic materials arepreferred for treatment in accordance with the present method and,accordingly, primary reference hereinafter will be made to the treatmentof cellulosic materials. The textile materials treated may be in anyconvenient form, such as fibers, threads, yarns, woven fabric, non-wovenfabric, knitted fabric, or

3,505,003 Patented Apr. 7, 1970 the like. At the time of treatment, thefabric may be in the unfinished state or it may have been previouslybleached, dyed, printed, or otherwise treated.

It is believed that the modification of the properties of the textilematerials which is achieved in accordance with the present inventionresult from a crosslinking reaction, wherein the vinyl phosphoniumcompounds of the present invention function as crosslinking agents. Inthis reaction, these vinyl phosphonium compounds react with thefunctional groups of the textile being treated, such as with thehydroxyl groups of a cellnlosic material.

The alkyl vinyl phosphonium halides for use in the method of the presentinvention may be prepared by reacting trivinyl phosphine with an alkylhalide, such as methyl iodide. This preparation is reported in theJournal of the American Chemical Society, volume 79 page 5887. Typicalspecific alkyl vinyl phosphonium halides, falling within the genericformula which has been set forth hereinabove include methyl trivinylphosphine iodide, ethyl trivinyl phosphine iodide, butyl trivinylphosphine iodide, pentyl trivinylphosphine bromides, hexyl trivinylphosphine chlorides, dimethyl divinyl phosphonium iodide, dibutyldivinyl phosphonium iodide, methyl trivinyl phosphonium chloride, andthe like. Of these, the preferred compound for use in the presentinvention has been found to be methyl trivinyl phosphonium iodide.Accordingly, primary reference hereinafter will be made to thismaterial.

The alkyl vinyl phosphonium halide may be applied to the textilematerial to be treated in any suitable formulation, for example, as anemulsion or as a solution. Additionally, it may conveniently be appliedby dipping, spraying, rolling, padding, or by other suitable applicationtechniques as are known to those in the art. Following the applicationof the phonsphonium halide modifier, the excess chemical solution may beremoved from the textile material by squeezing, centrifuging, pressing,or other similar operations. Thereafter, the material may be dried, ifdesired, using any convenient drying method, such as a forced air oven,infrared lamps, or evaporation in air at room temperature. Following thedrying step, where one is used, the treated fabric is then cured toeffect reaction between the modifying agent and the cloth. Dependingupon the curing temperatures used, the curing times may take from lessthan a minute at elevated temperatures, to several hours or more wherelow temperatudes, e.g., room temperatures are used.

Additionally, it has been found to be desirable to employ a basiccatalyst, with the phonsphonium halide modifying material of the presentinvention, to assist the reaction between the vinyl phosphonium halideand the textile material. Although the catalyst may be applied to thetextile material in a separate application step, either before or afterthe application of the alkyl vinyl phonsphonium halide, it is generallypreferred that the basic catalyst be incorporated as a component of thetextile treating formulation with the vinyl phosphonium halide. Whenthis is done, the basic catalyst is preferably utilized in an amountwhich will provide pH in the textile treating formulation of at leastabout 7 and preferably provide a pH within the range of about 8 to 11.

Various basic material which will provide a desired alkalinity in thetreating formulation, without adversely effecting either the treatingformulation itself or the textile material treated, may be used. In manyinstances, basic catalysts such as the alkali metal carbonates andbicarbonates including sodium carbonate, potassium carbonate, sodiumbicarbonate, potassium bicarbonate, and the like, as well as the alkanolamines, including the mono-, di-, and tri-, alkanol amines, such astriethanolamine, tributanolamine, dimethanolamine, dipropanolamine, arepreferred. Although, in some instances, the more basic alkali, such asthe alkali metal hydroxide and oxides, may be used, for reasons notclearly understood at the present time, it has surprisingly been foundthat the crease and wrinkle resistance obtained when using thesecatalyst is frequently not as great as that obtained when using thepreferred catalyst materials indicated hereinabove. Accordingly,hereinafter, primary reference will be made to sodium carbonate, sodiumbicarbonate, and triethanolamine, as being the preferred basic catalystmaterial for use in the present method.

As has been noted hereinabove, the treating formulations for use in thepresent method are preferably aqueous solutions. Desirably, thesesolutions will contain the alkyl vinyl phosphonium halide modifyingagent in amounts within the range of about 1 to about 40% by weight ofthe treating solution. In many instances, it has been found that amountsof these modifying agents within the range of about 10 to about 25% byweight of the treating so ution are preferred. Additionally, the basiccatalyst is desirably present in the solution in amounts within therange of about 0.5 to about 20% by weight of the treating formulationand in many instances it has been found that molar ratios of thecatalyst to the alkyl vinyl phosphonium iodide material within the rangeof about 0.2 to about 5:1 are preferred.

As set forth hereinabove, the treating formulations are applied to thetextile materials using any suitable method. Thereafter, excessformulation is removed from the material, and it may then be dried,after which it is cured to effect the reaction of the vinyl phosphoniumhalide with the textile. Although the curing may be effected bymaintaining the treated fabric at temperatures from about roomtemperature, i.e., about 20 centigrade, up to about 250 centigrade for aperiod of time sufficient to effect the desired reaction in the textilematerial, in many instances, it has been found to be preferable to carryout the curing at temperatures within the range of about 150 to about185 degrees centigrade for a period of from about 3 to 15 minutes.Although so-called cold curing, i.e. at

about room temperature, may be utilized in some instances, it has beenfound that frequently this type of curing does not give as good wrinkleresistance as curing operations carried out at higher temperatures.

Generally, it has been found that the treatment of the textile materialsshould be carried out under conditions and with treating formulationssuch that the treated textile material, after curing and removal ofunreacted modifying agents from the textile material has a resin orchemical add-on of from about 1 to 30% by weight of the textilematerial. In many instances, add-ons within the range of about 3 toabout 15% by weight of the textile material have been found to bepreferred. It is to be appreciated that the term add-on as used herein,refers to the modifying agent which has reacted with the textilematerial and remains as an integral chemical part of the textilematerial after the material has been cured and then washed to remove anyunreacted excess.

If desired, the textile treatment with the alkyl vinyl phosphoniumhalide compounds of the present invention may be supplemented bytreatment with the hand modifier or builder, a softener, a waterrepellant agent, a dyestuff, or other materials which may furtherenhance wrinkle resistance or impart or improve other desirableproperties in the fabric. Such additional modifying agents may beapplied simultaneously, i.e., in the same formulation as the vinylphosphonium halide compounds, or they may be applied to the fabricbefore or after the application of the vinyl phosphonium modifiers ofthe present invention.

In order that those skilled in the art my better understand the presentinvention and the manner in which it may be practiced, the followingspecific examples are given. In these examples, unless otherwiseindicated, temperatures are in degrees centigrade and parts and percentsare by weight. It is to be appreciated, however, that these examples areintended merely as being exemplary of the present invention and are notto be taken as a limitation thereof.

EXAMPLE 1 A swatch of bleached desized, mercerized x 80 threads perinch), cotton print cloth weighing 3.1 ounces per sq. yard, was paddedthrough an aqueous solution containing 20% by weight of methyl trivinylphosphonium iodide and sodium bicarbonate in a 1:1 mole ratio with themethyl trivinyl phosphonium iodide. This treating solution had a pH ofabout 8. Thereafter, the fabric was cured for 10 minutes at 160centigrade, using a forced air oven. The fabric was then hand washed inhot soapy water, rinsed, and pressed flat and dried. The add-on in thefabric was 12.5%. Thereafter, the wrinkle recovery angles of the clothwere determined, using the Monsanto method. The wrinkle recovery anglesin the fill direction were found to be 119, dry, and 124, wet, ascompared to 67, dry, and 83, wet, for an untreated control.Additionally, in a test for flame resistance, strips of the treatedfabric were held in a horizontal position and ignited. After removal ofthe flame source, there was no propagation of the flame, and the stripswere free from after-glow.

The replacement of methyl trivinyl phosphonium iodide in the aboveexamples with an aqueous solution of ethyl trivinyl phosphonium iodideresults in a cloth having comparable wrinkle resistance and flameresistance.

EXAMPLE 2 The procedure of Example 1 was repeated with the exceptionthat sodium carbonate, in a mole ratio of 0.5 mole of sodium carbonateto 1 mole of the methyl trivinyl phosphonium iodide was utilized as acatalyst. The treating solution had a pH of 10 and the add-on of thefabric, after curing as in Example 1 was 10.9%. The wrinkle recoveryangles in the fill direction, were found to be 133, dry, and wet, ascompared to 67, dry, and 83, wet, of an untreated control.

EXAMPLE 3 The procedure of Example 2 was repeated with the exceptionthat the sodium carbonate catalyst was used in a molar ratio of 1.5moles of sodium carbonate to 1 mole of methyl trivinyl phosphoniumiodide and the treating solution contained only 15% by weight of themethyl trivinyl phosphonium iodide. After impregnating the cloth as inthe preceding example, the fabric was cured for 10 minutes at 183centigrade and after washing and drying and pressing, there was anadd-on to the cloth of 8.5%. The wrinkle recovery angles of thethus-treated cloth was found to be 128, dry, and 126, wet, as comparedto 67, dry, and 83, wet, for the untreated control.

EXAMPLE 4 The procedure of Example 3 was repeated with the exceptionthat the catalyst used was triethanol amine, which material was added tothe treating solution in an amount of 0.51 mole of the amine per mole ofthe methyl trivinyl phosphonium iodide. The pH of the treating solutionin this instance was 10. The treated cloth was cured for 2 minutes atcentigrade and there was obtained an add-on of 5.7%. The wrinklerecovery angles for this cloth was determined to be 146, dry, and 136,wet, as compared to 67, dry and 83, wet, for an untreated control.

EXAMPLE 5 A treating solution was prepared containing 17% of the methyltrivinyl phosphonium iodide. This solution was applied to the fabric asin Example 1. Thereafter, the fabric was dried and a 10% by weightsolution of sodium hydroxide was applied to the dried fabric using akiss pad. The amount of sodium hydroxide solution applied was such thatit provided a mole ratio of sodium hydroxide to methyl trivinylphosphonium iodide on the fabric of about 4:1. Thereafter, the cloth wasplaced in a polyethylene bag, held for 30 minutes at 77 Fahrenheit andthen washed, and pressed. The wrinkle. recovery an gles of this clothwere determined to be 98, dry, and 127, wet, as compared to 67, dry and83, wet, for an untreated control.

Following the general procedure of Examples 1 through 4, dimethyldivinyl phosphonium bromide; hexyltrivinylphosphonium iodide; butyltrivinylphosphonium iodide; and methyl trivinylphosphonium chloride,employed in place of the methyl trivinylphosphonium iodide described,produced textile materials having improved wrinkle and flame-resistance.

What is claimed is:

1. A method for imparting improved wrinkle and flame resistance totextile materials having functional groups capable of reacting withactivated vinyl groups which comprises reacting said textile material ata pH of from about 7 to about 11 with at least about 1 percent by weightof an alkyl vinyl phosphonium salt having the formula:

wherein R is a lower alkyl group having from 1 to 6 carbon atoms, X ishalogen and n is a number from 1 to 2, said reaction conducted in thepresence of a basic catalyst.

2. The method as claimed in claim 1 wherein the alkyl vinyl phosphoniumsalt is methyl trivinyl phosphonium iodide.

3. The method as claimed in claim 2 wherein the textile material treatedis a cellulosic textile and the basic catalyst is applied simultaneouslywith the methyl triviny phosphonium iodide.

4. The method as claimed in claim 3 wherein the basic catalyst isselected .from the group consisting of alkali metal carbonates, alkalimetal bicarbonates and lower mono-, diand trialkanol amines, each alkylgroup of which contain from 1 to 4 carbon atoms.

5. A textile material, having functional groups capable of reacting withactivated vinyl groups, reacted with from about 1 to about 30 percent byweight of an alkyl vinyl phosphonium salt having the formula:

wherein R is a lower alkyl group having from 1 to 6 carbon atoms, X ishalogen and n is a number from 1 to 2.

6. The textile material as claimed in claim 5 wherein the alkyl vinylphosphonium salt is methyl trivinyl phosphonium iodide.

7. The textile material as claimed in claim 6 wherein the textilematerial is a cellulosic textile.

8. A formulation suitable for imparting wrinkle and flame resistance totextile materials having functional groups capable of reacting withactivated vinyl groups consisting essentially of an aqueous solution offrom about 1 to about 40 percent by weight of an alkyl vinyl phosphoniumsalt having the formula:

wherein R is a lower alkyl group containing from 1 to 6 carbon atoms, Xis halogen and n is a number from 1 to 2, and a basic catalyst presentin an amount sufiicient to impart a pH of at least about 7 to saidformulation.

9. The textle treating formulation as claimed in claim 8 wherein thealkyl vinyl phosphonium salt is methyl trivinyl phosphonium iodide andthe basic cata yst is selected from the group consisting of alkali metalcarbonates, alkali metal bicarbonates and alkanol amines.

10. The textile treating formulation as claimed in claim 9 wherein themethyl trivinyl phosphonium iodideis present in an amount within therange of about 1 to 40% by Weight of the treating solution and thecatalyst is present in a mole ratio of from about 0.2 to 5 moles permole of the phosphonium iodide.

References Cited UNITED STATES PATENTS 2,032,097 2/1936 Piggottetal 8-842,044,099 6/1936 Piggott 6t al. 884 2,746,836 5/1956 Rossin 8-84 XR3,212,842 10/1965 Burkitt s 3,251,642 5/1966 Valentine et al. 8116 XRMAYER WEINBLAT'I, Primary Examiner U.S.Cl.X.R.

